Nonlinear optical chiral compounds and devices incorporating same

ABSTRACT

The present disclosure is in part directed to optical devices for modulating light comprising compounds which spontaneously align. The disclosure is also directed to electro-optic compounds wherein chromophore substituents are chemically bound to a chiral polymer. In one embodiment, the chiral polymer comprises a binaphthyl monomeric unit.

RELATED APPLICATION INFORMATION

[0001] This application claims the benefit of priority to U.S.Provisional Application Serial No. 60/301730, filed Jun. 28, 2001; andto U.S. Provisional Application Serial No. 60/347127, filed Jan. 9,2002.

INTRODUCTION

[0002] Advances in polymeric electro-optic materials and devicefabrication techniques have increased the potential of these materialsand devices incorporating them, respectively, such as electro-opticmodulators, waveguides and fiber optic cores. Polymeric electro-opticmaterials have potential advantages over traditional inorganicmaterials, which may include larger band widths, better integration withoptical circuits, ease of fabrication, and lower operating voltages.

[0003] For fabrication of electro-optical devices, a polymeric materialshould have high thermal, chemical, and mechanical stability. Potentialapplications of electro-optic compounds and composites may require thatthe material possesses non-linear optical properties, includingnonlinear polarization. Molecular or microscopic optical non linearpolarization can be expressed as a power series of the electric field:

p ₁ =αE _(j) +βE _(j) E _(k) +γE _(j) E _(k) E _(l)+ . . .

[0004] where α is the linear polarizability, β is the firsthyperpolarizability, and γ is the second hyperpolarizability.Polarizability is directly related to the index of refraction. Moleculesof acentric dipolar symmetry are usually required for second-ordernonlinear optical behavior. Typical chromophores which display anon-zero β are charge-transfer molecules which have the general formula:(electron donor)(π-electron bridge)(electron acceptor).

[0005] To maintain a stable dipole alignment for electro-opticaldevices, high glass transition temperature (T_(g)) polymers withnonlinear optical chromophores incorporated as side chains orcross-linkable polymers with nonlinear optical chromophores which areembedded in or covalently bound to a polymer have been used. The hostpolymers in these systems may not contribute to optical microscopic ormacroscopic nonlinearity: the optical non-linearity stems from theπ-electron structure of the chromophore.

[0006] For macroscopic electro-optic activity to be finite, achromophore/polymer system must exhibit net acentric, ornon-centrosymmetric, order. The second-harmonic signals indicative ofnonlinear optical response arise from the quadratic response of thesample to an electric field, such as a laser beam. This response isrepresented by the nonlinear (macroscopic) polarization${P_{i}\left( {2\omega} \right)} = {\sum\limits_{j,k}{\chi_{ijk}{E_{j}(\omega)}{E_{k}(\omega)}}}$

[0007] where ijk refer to the Cartesian coordinates, E_(j)(ω) and E_(k)(ω) are the components of the optical field at the fundamentalfrequency, x_(ijk) is a component of the second-order nonlinearsusceptibility tensor x⁽²⁾, and P_(i)(2ω) is a component of thenonlinear source polarization at the second-harmonic frequency. Forsufficiently thin samples of electro-optic material, the polarizationmay lead to a amplitude of the second-harmonic field E(2ω) which mayvary linearly with thickness. For device use, a chromophore/polymersystem should have significant nonlinear optical (NLO) orelectro-optical (EO) coefficients.

[0008] Macroscopic acentric order is most commonly introduced by anelectric field that orients the molecules in a single direction. Methodsto achieve macroscopic noncentrosymmetry, in for example,chromophore/polymer systems include electric field poling, crystalgrowth, self-assembly, and deposition of Langmuir-Blodgett (LB) films.Such molecularly oriented polymers, however, may exhibit defects due togradual weakening of the orientation and a smaller nonlinear effect dueto the heat motion of the molecular chains.

[0009] Electric field poling usually involves applying an externalelectric field to break the isotropic symmetry of the polymers, duringwhich the NLO dye chromophores are aligned by coupling to their dipolemoment. This poling procedure may impose noncentrosymmetry on thepolymer material. The desired noncentrosymmetry may be most easilyinduced at temperatures close to the glass transition temperature,T_(g), of the polymer because of the increased mobility of the NLO dyemolecules in the softening polymer matrix. Cooling may then be performedin the presence of the applied electric field, which results in theformation of a polymer glass at the lower temperatures. For poledsystems, optical loss maybe present due in part to surface damage ofpolymer films and chromophore migration.

[0010] For optical device use, a polymer containing, for example, quasione-dimensional nonlinear optical chromophores, may be spincoated onto asolid substrate to yield thin films. Subsequently, the polymer film ispoled, resulting in polar ordering of the one-dimensional moleculesalong the film normal, yielding films which, for example, may have aC_(∞ν)symmetry. Such poled samples may be thermodynamically unstable,and eventually they may return to their original isotropiccentrosymmetric state. Further, these poled achiral polymers may nothave polarization corresponding to the x_(xyz) component of themicroscopic susceptibility.

[0011] Accordingly, there is a need for electroptical polymericmaterials which have enhanced optical properties. Further, materialsthat may exhibit these macroscopic properties without significant postprocessing, such as poling, would have substantial advantages in devicessuch as waveguides and modulators.

SUMMARY

[0012] The present invention is in part directed to chiral, or opticallyactive, polymers which are useful for optical devices, electro-opticcompounds and compositions. In one embodiment, an optical device isprovided which comprises an optically active compound comprising achromophore and a polymer, where either the chromophore or the polymeris chiral, or both are chiral, and where the chromophore undergoesspontaneous alignment.

[0013] In one embodiment, the optically active compound may have D_(n)symmetry, wherein n is equal to, or greater than, 2. In anotherembodiment, the optically active compound may be helical.

[0014] In another embodiment, the optically active compound comprises apolymer comprising one or more monomeric units comprising a binaphthylmoiety and a chromophore chemically bonded to a least one of saidmonomeric units, where the optically active compound has anon-centrosymmetric symmetry. The binaphthyl moiety may be selected fromthe group consisting of a binaphthyl structure, a binaphthol structure,a 1,1′-binaphthyl-2-ol-2′-amine structure, and a1,1′-binaphthyl-2,2′-diamine structure. The monomeric units may furthercomprise an alkyl moiety linked to the binaphthyl moiety. In oneembodiment, the alkyl moiety comprises an alkynyl group.

[0015] In another embodiment, the optically active compound may berepresented a chromophore chemically bonded to a polymer, where amonomeric unit of the polymer may be represented by formula I or II:

[0016] wherein Y represents independently for each occurrence a bond,alkyl, alkenyl, or alkynyl;

[0017] R₁ represents independently for each occurrence H, alkyl, oralkoxy;

[0018] R₂ represents independently for each occurrence N(R₁),O, S, Se oralkylene;

[0019] R₃ represents independently for each occurrence H, alkyl, or achromophore;

[0020] R₄ represents independently for each occurrence H, alkyl or achromophore; and

[0021] q is in the range 1 to 7 inclusive.

[0022] In one embodiment, one or more chromophores are covalently bondedto a monomeric subunit of the compound. In another embodiment, one ormore chromophores are covalently bonded to one or more monomericsubunits of the compound. In yet another embodiment, one or morechromophores are covalently bonded to substantially all monomeric unitsof the compound.

[0023] In another embodiment, the percentage of monomeric unitsfunctionalized by one or more chromophores is greater than about 3%,greater than about 7%, or even greater than about 10%. The monomericunits of the chiral polymers may be functionalized with one or morechromophores which may be covalently bonded to alternating or randommonomeric units.

[0024] Each monomeric unit of the nonlinear optical compound may befunctionalized by one or more of the same chromophore, or each monomericunit of the compound may be functionalized by differing chromophores.One monomeric unit may be functionalized by two differing chromophores.

[0025] In another embodiment, a nonlinear optical polymer is representedby structures with formula I or II:

[0026] wherein Y represents independently for each occurrence a bond,alkyl, alkenyl, or alkynyl;

[0027] R₁ represents independently for each occurrence H, alkyl, oralkoxy;

[0028] R₂ represents independently for each occurrence N(R₁),O, S, Se oralkylene;

[0029] R₃ represents independently for each occurrence H, alkyl, or achromophore;

[0030] R₄ represents independently for each occurrence H, alkyl or achromophore;

[0031] q is in the range 1 to 7 inclusive; and

[0032] n is an integer from 1 to about 100

[0033] In one embodiment, n is 1 to about 100. In another embodiment, nis 1 to about 50; in another embodiment, n is about 5 to about 50; andin a further embodiment, n is about 10 to about 50.

[0034] In one embodiment, the polymer is represented by the structure:

[0035] wherein CHR represents independently for each occurrence achromophore;

[0036] p is the range 0 and 7 inclusive;

[0037] x is 1 to about 50; and

[0038] n is about 10 to about 50.

[0039] In one embodiment, the polymer may exhibit an electro-opticcoefficient of greater than about 10 pm/V.

BRIEF DESCRIPTION OF THE FIGURES

[0040]FIG. 1a depicts schematically a helical polymer with nonlinearoptical chromophores attached as side groups.

[0041]FIG. 1b depicts a helical polymer with nonlinear opticalchromophores directly incorporated into the helical backbone.

[0042]FIG. 2 depicts an exemplary synthetic route to an exemplarymonomer 4.

[0043]FIG. 3 depicts an exemplary synthetic route to an exemplarymonomer 8.

[0044]FIG. 4 depicts an exemplary synthetic route to an exemplarymonomer 10.

[0045]FIG. 5 depicts an exemplary synthetic route to an exemplarymonomer 12.

[0046]FIG. 6 depicts an exemplary synthetic route to an exemplarymonomer 13.

[0047]FIG. 7 depicts an exemplary synthetic route to an exemplarypolymer PPOL 1.

[0048]FIG. 8 depicts an exemplary synthetic route to exemplary polymersPPOL 2 and PPOL 3.

[0049]FIG. 9 depicts an exemplary synthetic route to an exemplarychromophore functionalized polymer.

[0050]FIG. 10 depicts an exemplary synthetic route to an exemplaryelectron acceptor of a chromophore.

[0051]FIG. 11 depicts an exemplary synthetic route to an exemplarychromophore.

[0052]FIG. 12 depicts exemplary chiral helical structures.

[0053]FIG. 13 depicts the second harmonic signal intensity vs. thickness(μm) for films of the chiral helical polymer 41 depicted in FIG. 12.

DETAILED DESCRIPTION

[0054] A. Overview

[0055] The present disclosure is in part directed to chiral, oroptically active, polymers which are useful for electro-optic compoundsand compositions. In one embodiment, chromophore substituents may becovalently bound to an optically active polymer. In one embodiment, achromophore is covalently bonded to a chiral polymer. In anotherembodiment, a chiral chromophore is bonded to an achiral or a chiralpolymer, wherein the chiral chromophore induces chirality in theresulting electro-optic compound. In yet another embodiment, thenonlinear optical compound has a helical configuration.

[0056] In an aspect of the present disclosure, a device for modulatinglight comprises a compound or composition of the present disclosure.

[0057] B. Definitions

[0058] For convenience, before further description, certain termsemployed in the specification, examples, and appended claims arecollected here. These definitions should be read in light of thereminder of the disclosure and understood as by a person of skill in theart.

[0059] The articles “a” and “an” are used herein to refer to one or tomore than one (i.e. to at least one) of the grammatical object of thearticle. By way of example, “an element” means one element or more thanone element.

[0060] The term “alkyl” is art-recognized, and includes saturatedaliphatic groups, including straight-chain alkyl groups, branched-chainalkyl groups, cycloalkyl (alicyclic) groups, alkyl substitutedcycloalkyl groups, and cycloalkyl substituted alkyl groups. In certainembodiments, a straight chain or branched chain alkyl has about 30 orfewer carbon atoms in its backbone (e.g., C₁-C₃₀ for straight chain,C₃-C₃₀ for branched chain), and alternatively, about 20 or fewer.Likewise, cycloalkyls have from about 3 to about 10 carbon atoms intheir ring structure, and alternatively about 5, 6 or 7 carbons in thering structure.

[0061] The term “aralkyl” is art-recognized, and includes alkyl groupssubstituted with an aryl group (e.g., an aromatic or heteroaromaticgroup).

[0062] The terms “alkenyl” and “alkynyl” are art-recognized, and includeunsaturated aliphatic groups analogous in length and possiblesubstitution to the alkyls described above, but that contain at leastone double or triple bond respectively.

[0063] Unless the number of carbons is otherwise specified, “loweralkyl” refers to an alkyl group, as defined above, but having from oneto ten carbons, alternatively from one to about six carbon atoms in itsbackbone structure. Likewise, “lower alkenyl” and “lower alkynyl” havesimilar chain lengths.

[0064] The term “chiral” refers to asymmetric molecules, polymers,residues, or moieties thereof, the mirror images of which arenonsuperimposable and which are related like right and left hands. Eachmirror image is referred to herein as an “enantiomer”. Chiral materialsare characterized as exhibiting “optical activity”, which refers to theability to change the direction of the plane of polarized light toeither the right or left as it passes through the material. The term“chiral polymer” refers to an optically active polymer.

[0065] The terms “heterocyclyl” and “heterocyclic group” areart-recognized, and include 3- to about 10-membered ring structures,such as 3- to about 7-membered rings, whose ring structures include oneto four heteroatoms. Heterocycles may also be polycycles. Heterocyclylgroups include, for example, thiophene, thianthrene, furan, pyran,isobenzofuran, chromene, xanthene, phenoxathiin, pyrrole, imidazole,pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine,pyridazine, indolizine, isoindole, indole, indazole, purine,quinolizine, isoquinoline, quinoline, phthalazine, naphthyridine,quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline,phenanthridine, acridine, pyrimidine, phenanthroline, phenazine,phenarsazine, phenothiazine, furazan, phenoxazine, pyrrolidine, oxolane,thiolane, oxazole, piperidine, piperazine, morpholine, lactones, lactamssuch as azetidinones and pyrrolidinones, sultams, sultones, and thelike. The heterocyclic ring may be substituted at one or more positionswith such substituents as described above, as for example, halogen,alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, —CF₃, —CN, or thelike.

[0066] The terms “polycyclyl” and “polycyclic group” are art-recognized,and include structures with two or more rings (e.g., cycloalkyls,cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls) in which twoor more carbons are common to two adjoining rings, e.g., the rings are“fused rings”. Rings that are joined through non-adjacent atoms, e.g.,three or more atoms are common to both rings, are termed “bridged”rings. Each of the rings of the polycycle may be substituted with suchsubstituents as described above, as for example, halogen, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, —CF₃, —CN, or thelike.

[0067] The term “carbocycle” is art recognized and includes an aromaticor non-aromatic ring in which each atom of the ring is carbon. Theflowing art-recognized terms have the following meanings: “nitro” means—NO₂; the term “halogen” designates —F, —Cl, —Br or —I; the term“sulfhydryl” means —SH; the term “hydroxyl” means —OH; and the term“sulfonyl” means —SO₂ ⁺.

[0068] The terms “amine” and “amino” are art-recognized and include bothunsubstituted and substituted amines, e.g., a moiety that may berepresented by the general formulas:

[0069] wherein R50, R51 and R52 each independently represent a hydrogen,an alkyl, an alkenyl, —(CH₂)_(m)—R61, or R50 and R51, taken togetherwith the N atom to which they are attached complete a heterocycle havingfrom 4 to 8 atoms in the ring structure; R61 represents an aryl, acycloalkyl, a cycloalkenyl, a heterocycle or a polycycle; and m is zeroor an integer in the range of 1 to 8. In certain embodiments, only oneof R50 or R51 may be a carbonyl, e.g., R50, R51 and the nitrogentogether do not form an imide. In other embodiments, R50 and R51 (andoptionally R52) each independently represent a hydrogen, an alkyl, analkenyl, or —(CH₂)m—R61. Thus, the term “alkylamine” includes an aminegroup, as defined above, having a substituted or unsubstituted alkylattached thereto, i.e., at least one of R50 and R51 is an alkyl group.

[0070] The term “acylamino” is art-recognized and includes a moiety thatmay be represented by the general formula:

[0071] wherein R50 is as defined above, and R54 represents a hydrogen,an alkyl, an alkenyl or —(CH₂)m—R61, where m and R61 are as definedabove.

[0072] The term “amido” is art-recognized as an amino-substitutedcarbonyl and includes a moiety that may be represented by the generalformula:

[0073] wherein R50 and R51 are as defined above. Certain embodiments ofthe amide in the present invention will not include imides which may beunstable.

[0074] The term “carbonyl” is art-recognized and includes such moietiesas may be represented by the general formulas:

[0075] wherein X50 is a bond or represents an oxygen or a sulfur, andR55 represents a hydrogen, an alkyl, an alkenyl, —(CH₂)m—R61or a salt,R56 represents a hydrogen, an alkyl, an alkenyl or —(CH₂)m—R61, where mand R61 are defined above. Where X50 is an oxygen and R55 or R56 is nothydrogen, the formula represents an “ester”. Where X50 is an oxygen, andR55 is as defined above, the moiety is referred to herein as a carboxylgroup, and particularly when R55 is a hydrogen, the formula represents a“carboxylic acid”. Where X50 is an oxygen, and R56 is hydrogen, theformula represents a “formate”. In general, where the oxygen atom of theabove formula is replaced by sulfur, the formula represents a“thiocarbonyl” group. Where X50 is a sulfur and R55 or R56 is nothydrogen, the formula represents a “thioester.” Where X50 is a sulfurand R55 is hydrogen, the formula represents a “thiocarboxylic acid.”Where X50 is a sulfur and R56 is hydrogen, the formula represents a“thioformate.” On the other hand, where X50 is a bond, and R55 is nothydrogen, the above formula represents a “ketone” group. Where X50 is abond, and R55 is hydrogen, the above formula represents an “aldehyde”group.

[0076] The terms “alkoxyl” or “alkoxy” are art-recognized and include analkyl group, as defined above, having an oxygen radical attachedthereto. Representative alkoxyl groups include methoxy, ethoxy,propyloxy, tert-butoxy and the like. An “ether” is two hydrocarbonscovalently linked by an oxygen. Accordingly, the substituent of an alkylthat renders that alkyl an ether is or resembles an alkoxyl, such as maybe represented by one of —O-alkyl, —O-alkenyl, —O-alkynyl,—O—(CH₂)m—R61, where m and R61 are described above.

[0077] Substitutions may be made to alkenyl and alkynyl groups toproduce, for example, aminoalkenyls, aminoalkynyls, amidoalkenyls,amidoalkynyls, iminoalkenyls, iminoalkynyls, thioalkenyls, thioalkynyls,carbonyl-substituted alkenyls or alkynyls.

[0078] The definition of each expression, e.g. alkyl, m, n, etc., whenit occurs more than once in any structure, is intended to be independentof its definition elsewhere in the same structure unless otherwiseindicated expressly or by the context.

[0079] A list of the abbreviations utilized by organic chemists ofordinary skill in the art appears in the first issue of each volume ofthe Journal of Organic Chemistry; this list is typically presented in atable entitled Standard List of Abbreviations.

[0080] Certain monomeric subunits of the present disclosure may exist inparticular geometric or stereoisomeric forms. In addition, polymers andother compositions of the present disclosure may also be opticallyactive. The present invention contemplates all such compounds, includingcis- and trans-isomers, R- and S-enantiomers, diastereomers,(D)-isomers, (L)-isomers, the racemic mixtures thereof, and othermixtures thereof, as falling within the scope of the invention.Additional asymmetric carbon atoms may be present in a substituent suchas an alkyl group. All such isomers, as well as mixtures thereof, areintended to be included in this invention.

[0081] If, for instance, a particular enantiomer of a compound of thepresent invention is desired, it may be prepared by asymmetricsynthesis, or by derivation with a chiral auxiliary, where the resultingdiastereomeric mixture is separated and the auxiliary group cleaved toprovide the pure desired enantiomers. Alternatively, where the moleculecontains a basic functional group, such as amino, or an acidicfunctional group, such as carboxyl, diastereomeric salts are formed withan appropriate optically-active acid or base, followed by resolution ofthe diastereomers thus formed by fractional crystallization orchromatographic means well known in the art, and subsequent recovery ofthe pure enantiomers.

[0082] The terms ortho, meta and para are art-recognized and apply to1,2-, 1,3- and 1,4-disubstituted benzenes, respectively. For example,the names 1,2-dimethylbenzene and ortho-dimethylbenzene are synonymous.

[0083] The term ‘modulate’ is art-recognized, and refers to the process,or result of the process, of varying a characteristic of a carrier, forexample, light, which may be in accordance with an information bearingsignal.

[0084] It will be understood that “substitution” or “substituted with”includes the implicit proviso that such substitution is in accordancewith permitted valence of the substituted atom and the substituent, andthat the substitution results in a stable compound, e.g., which does notspontaneously undergo transformation such as by rearrangement,cyclization, elimination, or other reaction.

[0085] The term “substituted” is also contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described herein above. The permissible substituentsmay be one or more and the same or different for appropriate organiccompounds. For purposes of this invention, the heteroatoms such asnitrogen may have hydrogen substituents and/or any permissiblesubstituents of organic compounds described herein which satisfy thevalences of the heteroatoms. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

[0086] For purposes of this invention, the chemical elements areidentified in accordance with the Periodic Table of the Elements, CASversion, Handbook of Chemistry and Physics, 67th Ed., 1986-87, insidecover.

[0087] “Poling” is a term well-known in the art which refers to theprocess of aligning the individual dipole moments of a nonlinear opticalcomponent of a polymer by placing a large external electric field acrossthe material at an elevated temperature. The interaction with theelectric field causes a dipolar species to align in the direction of theapplied field. If the polymer is then cooled to its glassy state withthe field applied, the field induced non-centrosymmetric alignment isfrozen into place, and the material exhibits second-order nonlinearoptical properties. The poling process induces a polar axis in a polymerfilm.

[0088] The nonlinear hyperpolarisability β and nonlinear susceptibilityx⁽²⁾ are art-recognized tensors which are a function of the nonlinearoptical properties of a compound or medium. The nonlinear susceptibilitytensors may have certain forms of symmetry that reflect the structuralsymmetry of the medium. Accordingly, some tensor elements are zero andothers are related to each other, greatly reducing the total number ofindependent elements. For the tensor x⁽²⁾, there are 27 elements. Forexample, as known to someone skilled in the art, a compound or mediumwith the symmetry group D_(∞), corresponding to uniaxial alignment, hastensor elements of x which have non-vanishing components include x⁽²⁾_(xyz), x⁽²⁾ _(xzy), x⁽²⁾ _(yxz), and x⁽²⁾ _(yzx). A compound or mediumwith symmetry group D_(n) ( n>2 or n=2) has non vanishing components ofx corresponding to x⁽²⁾ _(ijk.) (with i not equal to j not equal to k).The symmetry group D₂, for example, corresponds to biaxial alignment.

[0089] C. Nonlinear Optically Active Compounds

[0090] In one embodiment, compounds which display non-centrosymmetricsymmetry may comprise chiral polymers which are functionalized with achromophore. In another embodiment, compounds which displaynon-centrosymmetric symmetry may comprise achiral polymers which arefunctionalized with a chiral chromophore. In an embodiment, thenonlinear optical compounds may have a helical configuration or haveD_(n) symmetry.

[0091] In an embodiment, the nonlinear optical compounds undergospontaneous alignment, for example, upon functionalization of a polymerwith a chromophore. Spontaneously aligned compounds may exhibitmacroscopic non-linear polarization, without, for example, an alignmentprocedure, for example, poling.

[0092] In one embodiment, the nonlinear optical compounds may be achiral bi-naphthyl based polymer functionalized with one or morechromophores. A chiral bi-naphthyl polymer may include any chiralpolymer with a bi-naphthyl moiety, for example, a bi-naphthyl basedmonomeric unit, a binaphthol based monomeric unit, or a1,1′-binaphthyl-2-ol-2′-amine based monomeric unit. In an embodiment,the chiral polymer functionalized with one or more chromophores may havemonomeric units comprising binaphthyl groups, binaphthol groups, or1,1′-binaphthyl-2-ol-2′-amine groups, or a combination of these groupswithin the same monomeric unit or in differing monomeric units. In oneembodiment, a monomeric unit of a chiral polymer functionalized with oneor more chromophores comprises a bi-naphthyl group linked to an alkyl,alkylene or alkynyl group or di-alkyl-phenyl group, wherein differingmonomeric units of a polymer may comprise differing or the same groups.A chiral bi-naphthyl based polymer functionalized with one or morechromophores may have one or more chromophores functionalized to atleast one monomeric unit. A chiral bi-naphthyl based polymerfunctionalized with one or more chromophores may have one or morechromophores functionalized to each monomeric unit.

[0093] In one embodiment, the chiral chromophore functionalizednonlinear optical compound, or the optically active compound may beformulas I or II:

[0094] wherein

[0095] Y is represents independently for each occurrence a bond, alkyl,alkenyl, or alkynyl;

[0096] R₁ represents independently for each occurrence H, alkyl, oralkoxy;

[0097] R₂ represents independently for each occurrence N(R₁), O, S, Seor alkylene;

[0098] R₃ represents independently for each occurrence H, alkyl, or achromophore;

[0099] R₄ represents independently for each occurrence H, alkyl, or achromophore;

[0100] at least one instance of R₃ or R₄ is a chromophore;

[0101] q is in the range 1 to 7 inclusive; and

[0102] n is 1 to about 1000.

[0103] In one embodiment, R₁ is hexyl. In another embodiment, R₃ ishexyl. In one embodiment, n is 1 to about 100. In yet anotherembodiment, R₃ and R₄ each independently may be an alkyl-chromophoremoiety, for example, an alkyl chain of 1 to about 10 carbons in length.

[0104] In another embodiment, q is the range 1 to 3 inclusive. In yetanother embodiment, q is 1.

[0105] In another embodiment, n is 1 to about 50, and anotherembodiment, n is about 5 to about 50, and in a further embodiment, n isabout 10 to about 50.

[0106] In yet another embodiment, a chromophore is covalently attachedto a chiral polymer through an alkoxy group or an amino group on thepolymer. In an embodiment, more than one chromophore is attached to amonomeric subunit of the chiral polymer. In another embodiment,substantially all monomeric units of the polymer are functionalized byone or more chromophores. In other embodiments, the percentage ofmonomeric units functionalized by one or more chromophores is greaterthan about 3%, greater than about 7%, or greater than about 10%. Inanother embodiment, the percentage of chromophores covalently bonded toa polymer is greater than about 3%, greater that about 7%, or evengreater than about 10% by weight of chromophore per total weight ofpolymer.

[0107] Each monomeric units of the nonlinear optical compound may befunctionalized by one or more of the same chromophore, or each monomericunit of the compound may be functionalized by distinct chromophores. Onemonomeric unit may be functionalized by two distinct chromophores.

[0108] In certain embodiments, the nonlinear optical chromophores arecovalently attached to the helical backbone as side-groups (FIG. 1a) ordirectly incorporated into the helical backbone of a polymer (FIG. 1b).This may result in a chiral molecular structure with very large(molecular) nonlinearity. Next, the polymer may spontaneously assume thenecessary D_(n) symmetry for nonlinear response in the bulk or in afilm. In one embodiment, helical nonlinear optical compoundsspontaneously assume a D_(n) symmetry when spincoated on a substrate. Inone embodiment, the polymers have liquid crystalline properties that mayprovide the necessary symmetry. This natural ordering may create athermodynamically stable system in which the nonlinearity does not decayas a function of time and temperature. The resulting structure may havea x_(xyz) susceptibility component that is useful for practicalapplications. These systems may have an antiparallel alignment of thechromophores which will not destroy the nonlinear optical response, forexample, in contrast to poled polymer films, since the presence of thexyz susceptibility does not require polar order.

[0109] In one embodiment, a chiral chromophore is linked to a non chiralpolymer backbone, creating a compound with non centrosymmetric symmetry.In another embodiment, the chiral chromophore functionalized polymer maybe racemic polybinaphthalene or poly(adamantylmethacrylate-methyl vinylisocyanate) or a maleimide-adamantyl methacrylate copolymer. In oneembodiment, the chiral chromophore functionalized polymer may be aflourinated chiral polymer, for example, poly (2-trifluoromethyladamantylacrylate-methyl vinyl isocyanate), poly (2-trifluoromethylperfluoro t-butyl acrylate-methyl vinyl isocyanate), and polymers basedon perfluoro esters. In another embodiment, the chiral chromophorefunctionalized polymer may assume a helical configuration.

[0110] In another embodiment, a polymer and a chromophore may form acomposition. In another embodiment, a polymer and chromophore may form amatrix. In yet another embodiment, a chromophore may be embedded in apolymer matrix, for example, a guest/host arrangement. In anotherembodiment, a chromophore may be used to cross-link polymer chains.

[0111] The polymer may contain one or two hydroxyl or amino functionalgroups per recurring monomeric unit. These functional groups can be usedto functionalize the polymer with one or more chromophores per monomericunit. In one embodiment, the chromophores are functionalized on thepolymer using Mitsunobu reaction conditions. In another embodiment, thechromophores are functionalized via an amino group. hi one embodiment,the compounds or composites have electro-optic coefficients which aregreater than 5 pm/V, greater than 10 pm/V, greater than 20 pm/V, greaterthan 30 pm/V or greater than 40 pm/V. In one embodiment, the compoundsor composites are stable at temperatures up to at least 150° C., atleast 200° C., or at least 250° C.

[0112] In another embodiment, methods of ordering the compounds orcomposites are, for example, stretching, formation of Langmuir-Blodgettfilms, or poling. In another embodiment, the macroscopic molecularorientation of the electro-optic compounds or compositions is controlledvia interference of polarization by multiphoton pathways, for example,by a laser.

[0113] In another embodiment, the chiral or helical polymers are poledto enhance the nonlinear optical response. In yet another embodiment,the optically active compounds are poled.

[0114] Spincoating may result in completely isotropic samples that donot allow second harmonic generation. Surprisingly, second harmonicgeneration or nonlinearity may be observed from these chiral polymers,after spincoating and without further processing. In the case of thehelicene molecules, they may organize into liquid crystalline-likelayers that stack together, giving rise to D₂- and D_(∞)-symmetry.

[0115] A polymer may be functionalized with a chromophore, creatingcompounds which may spontaneously assume a non-centrosymmetric symmetry.In one embodiment, compounds which display non-centrosymmetric symmetrymay comprise chiral polymers which are functionalized with achromophore. In another embodiment, compounds which displaynon-centrosymmetric symmetry may comprise polymers which arefunctionalized with a chiral chromophore.

[0116] A polymer may be any known polymer. Exemplary polymers includeboth chiral and achiral polymers, and include both aliphatic andaromatic polymers, including polyurethanes, polymethylmethacrylate,polyethers, polyetherimides, polyesters, polyimide, polymaleimides,poly(phenylquinoxalines), polyamic acid, polyamides, polysiloxanes,polyacrylates, polystyrene, polycarbonates derived from bisphenol, andpolysulfones derived from bisphenol A, poly(2-methoxy, 5 ethyl (2′hexyloxy) para-phenylene vinylene) (MEH), BaytronP (Pedot-PSS),BHEP-PPV, C₆₀-PCBM, and polycarbonate.

[0117] Representative natural polymers include proteins, such as zein,modified zein, casein, gelatin, gluten, serum albumin, or collagen, andpolysaccharides, such as cellulose, dextrans, hyaluronic acid, andpolymers of alginic acid.

[0118] Representative synthetic polymers include polyphosphazines,poly(vinyl alcohols), polyamides, polycarbonates, polyalkylenes,polyacrylamides, polyanhydrides, poly(phosphoesters), polyalkyleneglycols, polyalkylene oxides, polyalkylene terephthalates, polyvinylethers, polyvinyl esters, polyvinyl halides, polyvinylpyrrolidone,polyglycolides, polysiloxanes, polyphosphates and polyurethanes.

[0119] Synthetically modified natural polymers include alkyl celluloses,hydroxyalkyl celluloses, cellulose ethers, cellulose esters, andnitrocelluloses. Other like polymers of interest include, but are notlimited to, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose,hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, celluloseacetate, cellulose propionate, cellulose acetate butyrate, celluloseacetate phthalate, carboxymethyl cellulose, cellulose triacetate andcellulose sulfate sodium salt.

[0120] The polymers may be provided as copolymers or terpolymers, orpolymers with more than three species of monomers. The polymers may alsoinclude further subunits. These polymers may be obtained from chemicalsuppliers or synthesized from monomers obtained from these suppliersusing standard techniques. In certain embodiments, the polymers arecomprised almost entirely, if not entirely, of the same subunit. Inother embodiments, the polymers may be copolymers, in which differentsubunits and/or other monomeric units are incorporated into the polymer.In certain instances, the polymers are random copolymers, in which thedifferent subunits and/or other monomeric units are distributed randomlythroughout the polymer chain. In certain embodiments, the polymer is amethylmethacrylate copolymer.

[0121] In other embodiments, the different types of monomeric units aredistributed randomly throughout the chain. In part, the term “random” isintended to refer to the situation in which the particular distributionor incorporation of monomeric units in a polymer that has more than onetype of monomeric units is not directed or controlled directly by thesynthetic protocol, but instead results from features inherent to thepolymer system, such as the reactivity, amounts of subunits and othercharacteristics of the synthetic reaction or other methods ofmanufacture, processing or treatment.

[0122] In certain embodiments, the subject polymers may be cross-linked.For example, substituents of the polymeric chain, may be selected topermit additional inter-chain cross-linking by covalent or electrostatic(including hydrogen-binding or the formation of salt bridges), e.g., bythe use of a organic residue appropriately substituted. A chromophoremay be used for cross-linking subject polymers.

[0123] A polymer may have a chain terminating group, by which thepolymer terminates. Examples of such chain terminating groups includemonofunctional alcohols and amines.

[0124] The ratio of different subunits in a polymer may vary.Alternatively, in other instances, the polymers are effectively composedof two different subunits, in which the ratio of the subunits may varyfrom less than 1:99 to more than 99: 1, or alternatively 10:90, 15:85,25:75, 40:60, 50:50, 60:40, 75:25, 85:15, 90:10 or the like.

[0125] In certain embodiments, the polymeric chains of the subjectcompounds and compositions, e.g., which include repetitive elementsshown in any of the subject formulas, have molecular weights rangingfrom about 2000 or less to about 1,000,000 or more daltons;alternatively, ranging from about 10,000, 20,000, 30,000, 40,000, or50,000 daltons to about 1,000,000 daltons. In one embodiment, themolecular weight (Mw) is about 5000 to about 30000. Number-averagemolecular weight (Mn) may also vary widely, but generally fall in therange of about 1,000 to about 200,000 daltons, from about 1,000 to about40,000 daltons and, even from about 1,000 to about 20,000 daltons.Within a given sample of a subject polymer, a wide range of molecularweights may be present. For example, molecules within the sample mayhave molecular weights which differ by a factor of 2, 5, 10, 20, 50,100, or more, or which differ from the average molecular weight by afactor of 2, 5, 10, 20, 50, 100, or more. One method to determinemolecular weight is by gel permeation chromatography (“GPC”), e.g.,mixed bed columns, THF solvent, CH₂Cl₂ solvent, light scatteringdetector, and off-line dn/dc. Other methods are known in the art.

[0126] Plasticizers and stabilizing agents known in the art may beincorporated in the polymers or compounds of this disclosure.

[0127] In one embodiment, the polymer has a molecular weight whichallows formation of thin films, which may be about 0.1 to about 10 μmthick.

[0128] In another embodiment, the polymer has a high glass transitiontemperature to prevent decomposition of the polymer composition duringprocessing. In one embodiment, the polymer has a glass transitiontemperature (T_(g)) between about 90° C. and about 250° C., or betweenabout 110° C. and about 200° C.

[0129] In an embodiment, the polymers are chiral polymers. Chiralpolymers include chiral polyisocyanates, chiral polyisocyanides, chiralbinaphthyl-based polymers, chiral polyanilines, chiral polycarbonates,chiral polyisocyanides, chiral polyesters, chiral polyurethanes, chiralpoly(aryl)esters, chiral poly(aryl)ethers, including polyetherimides,polyethersulfones, and polyetherketones, cellulose, chiral polyphenylenevinylene (PPV), chiral liquid crystalline polymers or compounds, andhelicenes. Further chiral polymers include polymers comprising chiralspirobiindane moieties, chiral indane bisphenol moieties, and the like.

[0130] In a particular embodiment, the chiral polymers undergospontaneous alignment. In one embodiment, the chiral polymers assume ahelical configuration.

[0131] Chiral polymers may be polymers with symmetry groups D_(n), (n>2or n=2) D_(2d), C_(2v), C₂, C_(s), and C₁. In one embodiment, thepolymer has a D_(n) (n>2 or n=2) symmetry. In another embodiment, thepolymer has D_(∞) symmetry. In another embodiment, the symmetry of thechiral polymer is such that the second order macroscopic susceptibilitycomponent x_(xyz) is non-zero. In a particular embodiment, the chiralpolymers undergo spontaneous alignment, leading to a macroscopic chiralmedium with nonvanishing macroscopic second-order nonlinear opticalproperties.

[0132] In another embodiment, the chiral polymers exhibit macroscopicnonlinearity without application of a shearing force or an electricfield. In a further embodiment, the chiral polymers may be poled. In aneven further embodiment, a poled chiral polymer may exhibit differenthyperpolarizibility and different susceptibility components.

[0133] In one embodiment, a chiral polymer may be a bi-naphthyl basedpolymer. In an embodiment, a chiral polymer may have monomeric unitscomprising binaphthyl groups, binaphthol groups, or1,1′-binaphthyl-2-ol-2′-amine groups, or a combination of these groupswithin the same monomeric unit or in distinct monomeric units. In oneembodiment, a monomeric unit of a chiral polymer comprises a bi-naphthylgroup linked to an alkyl, alkylene or alkynyl group or di-alkyl-phenylgroup, wherein differing monomeric units of a polymer may comprisediffering or the same groups.

[0134] In an embodiment, a chiral polymer may include one or more ofrecurring monomeric units selected from the group of formula I and II:

[0135] wherein

[0136] Y represents independently for each occurrence a bond, alkyl,alkenyl, or alkynyl;

[0137] R₁ represents independently for each occurrence H, alkyl, oralkoxy;

[0138] R₂ represents independently for each occurrence N(R₁), O, S, Seor alkylene;

[0139] R₃ represents independently for each occurrence H or alkyl;

[0140] q is in the range 1 to 7 inclusive; and

[0141] n is 1 to about 1000.

[0142] In one embodiment, R₁ is hexyl. In another embodiment, R₃ ishexyl.

[0143] In one embodiment, n is 1 to about 100. In another embodiment, nis 1 to about 50, and another embodiment, n is about 5 to about 50, andin a further embodiment, n is about 10 to about 50.

[0144] In another embodiment, a chiral polymer may include one or moreof recurring monomeric units of selected from formula III or IV:

[0145] wherein:

[0146] R₁ represents independently for each occurrence H, alkyl oralkoxy;

[0147] R₂ represents independently for each occurrence N(R₁), O, S, Seor alkylene;

[0148] R₃ represents independently for each occurrence H or alkyl;

[0149] q is in the range 1 to 7 inclusive; and

[0150] n is 1 to about 1000.

[0151] In one embodiment, R₁ is hexyl. In another embodiment, R₃ ishexyl. In an embodiment, q is 1.

[0152] Chiral naphthyl based polymers may be prepared, for example, by aSuzuki coupling. Acetylenic derivatives of these polymers, for example,when Y is an acetylenic moiety, may be prepared via a Shinogashirareaction. Other methods of preparation which may be used include radicalpolymerization, and ionic polymerization.

[0153] A chromophore substituent is any substituent that exhibits anon-zero hyperpolarizablity β. Chromophores are charge-transfersubstituents which have the general formula: (electron donor)(π-electronbridge)(electron acceptor). A continuous π electron chain, or bridge,chemically connects the electron donor groups and electron acceptorgroups.

[0154] Exemplary chromophores include dyes, such as azo dyes; forexample, dyes based on azobenzene, macrocycles, and bridged di-arenes.Chromophores include tricyanodiphenoquinodimethane dyes and residues;for example, 7-[4-(dimethylamino)phenyl]-7,8,8-tricyanoquinodimethane,amino-nitro-azobenzene dyes/residues, dicyanovinyl dyes,tetracyanobutadiene dyes, [(nitrophenylazo)phenylazo]phenyl amine dyes,dicyanomethylene pyran dues and their residues, and imidiazolium dyesand their residues.

[0155] In one embodiment, the electron donor groups may comprise, forexample, —SH, -alkylthio, hydroxyl, alkyoxyl, alkyl, vinyl, halo, —NH₂,amino group and the like. In a particular embodiment, the electron donorgroups are aliphatic amines, aromatic amines, or combinations ofaliphatic and aromatic amines.

[0156] Electron accepting groups may comprise for example, nitro,haloalkyl, acyl, alkanoyloxy, alkoxysulfonyl, —CN, —NO₂, —COOH, —COCH₃,—CHO, —CONH₂, —CHC(CN)₂, —C(CN)C(CN)₂ and the like. In a particularembodiment, the chromophores have CN electron acceptor groups. In aparticular embodiment, the chromophore is bonded to a chiral polymer viaa electron donor group.

[0157] In a particular embodiment, the chromophore substituents orchromophores are represented by the structure:

R₅—R₄—R₂—R₃—R₂—R₇

[0158] wherein

[0159] R₁ represents independently for each occurrence H, alkyl,alkenyl, alkoxy, or hydroxyl;

[0160] R₂ represents independently for each occurrence alkynyl, alkenyl,or

[0161] wherein X represents for each occurrence N or C; and n is aninteger between 1 and 10 inclusive;

[0162] R₃ is selected from the group consisting of cycloalkenyls andunsaturated heterocycles;

[0163] R₄ is selected from the group consisting of:

[0164] R₅ is alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl,arylalkyl, heterocyclyl,

[0165] R₆ is alkyl, alkoxy or hydroxyl, including branched alkyls andalkoxyls exhibiting chirality;

[0166] R₇ is an electron acceptor group comprising at least one cyanogroup; and

[0167] the stereochemical configuration of a compound represented by 1may be E or Z at an olefin; R, or S at a stereocenter; or any mixture ofthese configurations.

[0168] In a certain embodiment, R₇ may be a pyran or pyranone moiety.

[0169] In a certain embodiment, the chromophore substituents orchromophores are represented by the structure:

[0170] wherein

[0171] R₁ represents independently for each occurrence H, alkyl,alkenyl, alkoxy, or hydroxyl;

[0172] R₂ represents independently for each occurrence alkenyl, oralkynyl;

[0173] R₃ is selected from the group consisting of:

[0174] R₄ is selected from the group consisting of:

[0175] R₅ is:

[0176] R₆ is alkyl, alkoxy or hydroxyl including branched alkyls andalkoxyls exhibiting chirality; and

[0177] the stereochemical configuration of a compound represented by 2may be E or Z at an olefin; R, or S at a stereocenter; or any mixture ofthese configurations.

[0178] In certain embodiments, the chromophore substituents orchromophores are represented by the structure:

[0179] wherein

[0180] R₁ represents independently for each occurrence H, alkyl alkenyl,alkoxy, or hydroxyl;

[0181] R₅ is:

[0182] R₆ is alkyl, alkoxy or hydroxyl, including branched alkyls andalkoxyls exhibiting chirality; and

[0183] the stereochemical configuration of a compound represented by 3may be E or Z at an olefin; R, or S at a stereocenter; or any mixture ofthese configurations.

[0184] In certain embodiments, the chromophores are selected from thegroup consisting of:

[0185] wherein

[0186] R₁ is H, alkyl or alkoxyl; and

[0187] R₂ is alkyl.

[0188] In certain embodiments, the chromophores are represented by:

[0189] wherein

[0190] R₁ is independently hydrogen, halogen, alkyl, cycloalkyl,alkenyl, cycloalkenyl, aryl, alkylaryl, or arylalkyl;

[0191] R₂ is independently hydrogen, halogen, alkyl, cycloalkyl,alkenyl, cycloalkenyl, aryl, alkylaryl, or arylalkyl;

[0192] R₃ represents independently for each occurrence H, halogen,alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, aryloxyalkyl, haloalkyl, or haloaryl;

[0193] R₄ represents independently for each occurrence H, halogen,alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, aryloxyalkyl, haloalkyl, or haloaryl; and

[0194] x and y are each independently 0 or an integer from 1 to 4.

[0195] In certain other embodiments, the chromophores are representedby:

[0196] wherein

[0197] R₁ is independently hydrogen, halogen, alkyl, cycloalkyl,alkenyl, cycloalkenyl, aryl, alkylaryl, or arylalkyl;

[0198] R₂ is independently hydrogen, halogen, alkyl, cycloalkyl,alkenyl, cycloalkenyl, aryl, alkylaryl, or arylalkyl;

[0199] R₃ represents independently for each occurrence H, halogen,alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, aryloxyalkyl, haloalkyl, or haloaryl;

[0200] R₄ represents independently for each occurrence H, halogen,alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, aryloxyalkyl, haloalkyl, or haloaryl; and

[0201] x and y are each independently 0 or an integer from 1 to 4.

[0202] In certain other embodiments, the chromophore may have asymmetry, chirality, or other optical property which upon bonding to apolymer or other moiety, renders that polymer or moiety chiral. Chiralchromophores may have chiral centers in the donor, acceptor or withinthe π electron bridge. Chiral chromophores which may induce chiral ornon-centrosymmetric symmetry when linked to an achiral polymer include:

[0203] wherein R₁ is alkyl or H; and the stereochemical configuration ofthese chromophores may be E or Z at an olefin; R, or S at astereocenter; or any mixture of these configurations.

[0204] D. Devices

[0205] Optical fibers incorporated with optical materials are disclosedin commonly owned U.S. patent application Ser. No. 09/903387, entitledMethod of Incorporating Optical Material Into an Optical Fiber, filedJul. 11, 2001, and is hereby incorporated by reference and forms part ofthis disclosure.

[0206] An optical device may be any device which propagateelectromagnetic waves with wavelengths in the optical region. Forexample, an optical device may be an optical waveguide which has a coreregion of higher refractive index surrounded by a region of lowerrefractive index, for example, cladding.

[0207] In an aspect of the present disclosure, an optical device isformed which comprises a substrate and at least one layer on saidsubstrate, said layer including a composition or compound of the presentdisclosure.

[0208] In an aspect of the present disclosure, a wavelength converter ofan optical waveguide type for propagating the fundamental wave comprisesa compound or composition of the present disclosure. In an embodiment,the device, which comprises compounds of the disclosure, is used tomodulate a beam of light. The modulation may be imposed on the phase,frequencey, amplitude, or direction of the modulated beam.

[0209] In an aspect of the present disclosure, a nonlinear opticaldevice of a waveguide structure comprising a light transmitting mediumas a waveguide in combination with an optical element, comprises ancompound or composite of the present disclosure. In one embodiment, thenonlinear optical device is capable of performing a switching operationby application of a modulated electric field.

[0210] In yet another aspect, the present disclosure is directed to anoptical waveguide structure comprising a light transmitting core and acladding material partially or entirely enclosing the core. The lighttransmitting core is an electro-optical polymeric material, as describedabove, containing an electro-optical chromophore in admixture with apolymer or chemically bonded to the polymer. The cladding material is aphotochromic polymeric material which exhibits a lower refractive indexrelative to that of the electro-optical polymeric material. Thephotochromic polymeric material comprises a second aliphatic or aromaticpolymer identical in structure with the first polymer and a chromophorecomponent.

[0211] In still another aspect, the present disclosure is directed to anoptoelectronics device comprising a substrate holding at least a portionof a first, elongate waveguide propagating an optical signal along apropagation axis thereof, and a second waveguide positioned in opticalproximity to the portion of the first waveguide. The optical waveguidestructure of the present invention described above forms the secondwaveguide of the optoelectronics device. The second waveguide has apropagation axis aligned with the propagation axis of the portion of thefirst waveguide. The second waveguide is used for coupling opticalenergy to or from the optical signal propagating in the first waveguide.

[0212] In yet another aspect, the present disclosure is directed to anoptical structure, typically an integrated optical structure, comprisingan optical circuit disposed atop a substrate. The optical circuitcomprises at least two optical devices and an optical waveguide, whereineach of the optical devices is optically coupled to and physicallyseparated by a portion of the optical waveguide. The optical waveguidestructure of the present invention described above is used as theoptical waveguide in the inventive optical structure.

[0213] In still another aspect, the present disclosure is directed to anoptoelectronics device comprising a substrate holding at least a portionof a first, elongate waveguide propagating an optical signal along apropagation axis thereof, and a second waveguide positioned in opticalproximity to the portion of the first waveguide.

[0214] The optical waveguide structure described above forms the secondwaveguide of the optoelectronics device. The second waveguide has apropagation axis aligned with the propagation axis of the portion of thefirst waveguide. The second waveguide is used for coupling opticalenergy to or from the optical signal propagating in the first waveguide.

[0215] In yet another aspect, the present disclosure relates to anoptical structure, typically an integrated optical structure, comprisingan optical circuit disposed atop a substrate. The optical circuitcomprises at least two optical devices and an optical waveguide, whereineach of the optical devices is optically coupled to and physicallyseparated by a portion of the optical waveguide. The optical waveguidestructure of the present invention described above is used as theoptical waveguide in the inventive optical structure.

[0216] In one embodiment the compounds of the present disclosure areused in an optical device which modulates light. In another embodiment,the compounds of the present invention are used in a device which actsas an optical switch. Other devices contemplated by the presentinvention include optical storage devices and frequency doublers.

[0217] In another embodiment, the compounds of the present disclosuremay be used in a polymer nano- or micro-structure on a semiconducting orinsulating surface.

[0218] In a further embodiment, the device is hermetically sealed orcomprises a nonoxidizing cladding layer which may prevent oxidization.In another further embodiment, a cladding layer may be used in a devicewhich may comprise either chiral or achiral components.

[0219] Advantages afforded by the optical waveguide structures of thepresent disclosure over present waveguides include higherelectro-optical coefficients, greater long-term stability, and easierprocessing.

EXEMPLIFICATION

[0220] The invention now being generally described, it will be morereadily understood by reference to the following examples, which areincluded merely for purposes of illustration of certain aspects andembodiments of the present invention, and are not intended to limit theinvention.

Example 1

[0221] Synthesis of S-(+)-6,6′-dibromo-[1,1′-binaphthalene] 2

[0222] In a round-bottomed flask of 500 ml, 10.0g (35.0 mmol) ofS-(−)-[1,1′-binaphthalene]-2,2′-diol 1 is dissolved in 200 ml ofdichloromethane and cooled down to −78° C. The flask is equipped with aCaCl₂-tube. Under vigorously stirring, 5.4 ml (105 mmol) of bromine,dissolved in 50 ml of dichloromethane, is dropwise added over 30minutes. The mixture is allowed to reach room temperature and 200 ml ofa NaHSO₃-solution (2 M) is added. The organic layer is washed two timeswith brine and dried over MgSO₄. After evaporation of the solvent, thecompound is collected as a grey solid.

[0223] Yield: 15.5g (100%); [a]_(D) ²⁵=+137 deg dm⁻¹ mol⁻¹ l (c=1.0 inCH₂Cl₂)

[0224]¹H-NMR (CDCl₃): δ(ppm): 8.07(d, J=1.5 Hz, 2H), 7.91 (d, 2H),7.42(dd, 2H), 7.28(d, 2H), 6.98(d, 2H), 5.03(s, 2H)

Example 2 Synthesis ofS-(−)-6,6′-dibromo-2′-hexyloxy-[1,1′-binaphthalene]-2-ol 3

[0225] Under argon atmosphere a solution of 14.4 g (32.4 mmol) of 2,dissolved in 70 ml of dry DMF, is slowly added to a suspension of 0.78 g(32.4 mmol) of NaH in 30 ml dry DMF. After 15 minutes, 4.6 ml (32.4mmol) of hexylbromide and 100 mg of anhydrous NaI is added. The mixtureis stirred overnight at 50° C. After cooling down, the mixture is pouredinto 200 ml of water and extracted with dichloromethane. The organiclayer is washed with a saturated NaHCO₃-solution, with brine and driedover MgSO₄. After removal of the solvents, the crude compound ispurified with column chromatography (silicagel; eluent:hexane/dichloromethane (60:40 v/v)) and isolated as an oil.

[0226] Yield: 8.2g (48%); [a]_(D) ²⁵=+32.4 deg dm⁻¹ mol⁻¹ l (c=0.06 inCHCl₃)

[0227]¹H-NMR (CDCl₃): δ(ppm): 8.05(d, J=1.5 Hz, 1H), 8.00 (d, J=1.5 Hz,1H), 7.93 (d, 1H), 7.80 (d, 1H), 7.46 (d, 1H), 7.34 (d, 1H), 7.34 (dd,1H), 7.28 (dd, 1H), 7.02 (d, 1H), 6.86 (d, 1H), 4.89 (d, 1H), 3.99 (m,2H), 1.43 (qu, 2H), 1.01 (m, 6H), 0.75 (t, 3H)

Example 3 Synthesis ofS-(−)-6,6′-dibromo-2-hexyloxy-2′-methoxymethoxy-[1,1′-binaphthalene] 4

[0228] Under argon atmosphere a solution of 5.28g (10.0 mmol) of 3,dissolved in 30 ml of dry THF, is slowly added to a suspension of 0.57 g(12.0 mmol) of NaH in 20 ml of dry THF. After 15 min, 0.90 ml (12.0mmol) of chloromethylmethylether is added very slowly and the mixture isstirred overnight at room temperature. The reaction mixture is pouredinto 100 ml of water and extracted with dichloromethane. The organiclayer is washed with a saturated NaHCO₃-solution, with brine and driedover MgSO₄. After removal of the solvents, the crude compound ispurified with column chromatography (silicagel; eluent:hexane/dichloromethane (60:40 v/v)) and isolated as an oil.

[0229] Yield: 4.70 g (82%); [a]_(D) ²⁵=−156 deg dm⁻¹ mol⁻¹ l (c=3.30 inCHCl₃)

[0230]¹H-NMR (CDCl₃): δ(ppm): 8.01 (d (br), 2H), 7.85 (d, 1H), 7.82 (d,1H), 7.56 (d, 1H), 7.42 (d, 1H), 7.34 (dd, 1H), 7.28 (dd, 1H), 7.00 (d,1H), 6.94 (d, 1H), 5.30(s, 1H), 5.07(d, 1H), 4.96 (d, 1H), 3.95 (m, 2H),3.17 (s, 3H), 1.37 (m, 2H), 1.0 (m, 6H), 0.73 (t, 3H)

Example 4 Synthesis of 1,4-dihexyloxybenzene 6

[0231] Under argon atmosphere, 6.90 g (300 mmol) of Na is reacted with200 ml of absolute ethanol. Then, 16.5 g (150 mmol) of hydroquinone 5 isadded, followed by 42.2 ml (300 mmol) of hexylbromide and 200 mg ofanhydrous NaI. The mixture is refluxed overnight. Ethanol is evaporatedunder reduced pressure and water (150 ml) is added. The product isextracted with dichloromethane and dried over MgSO₄. After filtration,the solvents are removed and the crude compound is recrystallized fromethanol.

[0232] Yield: 31.2 g (75%); m.p. : 45.5° C.

[0233]¹H-NMR (CDCl₃): δ(ppm): 6.82 (s, 4H), 3.89 (t, 4H), 1.72 (qu, 4H),1.4 (m, 12H), 0.90 (t, 6H)

Example 5 Synthesis of 2,5-dihexyloxy-1,4-dibromobenzene 7

[0234] In a round-bottomed flask of 500 ml, 27.8g (100 mmol) of 6 isdissolved in 300 ml of dichloromethane and cooled down to 78° C. Theflask is equipped with a CaCl₂-tube. Under vigorously stirring, 14.4 ml(280 mmol) of bromine, dissolved in 100 ml of dichloromethane, is slowlyadded. The mixture is allowed to reach room temperature and 400 ml ofNaHSO₃-solution (2 M) is added. The organic layer is washed with asaturated NaHCO₃-solution, with brine and dried over MgSO₄. Afterevaporation of the solvent, the compound is recrystallized from ethanol.

[0235] Yield: 38.0 g (87%); m.p. : 63.6° C.

[0236]¹H-NMR (CDCl₃):δ(ppm): 7.08 (s, 2H), 3.94 (t, 4H), 1.80 (qu, 4H),1.4 (m, 12H), 0.90 (t, 6H)

Example 6 Synthesis of 2,5-dihexyloxy-benzene-1,4-diboronic Acid 8

[0237] A solution of 6.53 g (15.0 mmol) of 7 in 80 ml of dry THF ispurged with argon and cooled to −78° C. 23 ml (54.0 mmol) of n-BuLi(2.34 M in hexane) is added. This mixture is stirred during 15 minutesand then dropwise added to a solution of 15 ml triethylborate in 20 mlof dry THF. The solution is allowed to reach room temperature andstirred overnight. Then, 150 ml of HCl (1 M) is added and the reactionmixture is vigorously stirred for 3 h. The precipitate is filtered off,washed thoroughly with water and dichloromethane and dried.

[0238] Yield: 38.0 g (87%);T_(m): 63.6° C.

[0239]¹H-NMR (CDCl₃): δ(ppm): 7.80 (s (br), 4H), 7.19 (s, 2H), 3.97 (t,4H), 1.72 (qu, 4H), 1.4 (m, 12H), 0.83 (t, 6H)

Example 8 Synthesis ofS-6,6′-di(trimethylsilylethynyl)-[1,1′-binaphthalene]-2,2′-diol 9

[0240] Prior to use, 2 is recrystallized from toluene/hexane. 11.1 g(25.0 mmol) of 2, 250 mg of Pd[PPh₃]Cl₂ and 500 mg of PPh₃ are dissolvedin 50 ml of dry piperidine. The solution is purged with argon and heatedto 40° C. Then, 9.9 ml (70.0 mmol) of trimethylsilylacetylene isinjected, followed by an argon purged solution of 200 mg of CuI and 1.0g of LiBr in 10 ml of dry THF. The reaction mixture is refluxed for 1 hunder argon atmosphere. After cooling, the mixture is poured into 400 mlof a HCl-solution (1 M) and extracted with dichloromethane. The combinedorganic layers are washed with a HCl-solution (1 M), with a saturatedNaHCO₃-solution, with brine and finally dried over MgSO₄. The solventsare removed and the crude product is purified by column chromatography(silicagel; eluent: ethylacetate/dichloromethane (30:70 v/v)). Thecompound is immediately used in the next step.

Example 9 Synthesis ofS-(+)-6,6′-diethynyl-[1,1′-binaphthalene]-2,2′-diol 10

[0241] A solution of 9 in 70 ml of methanol and 30 ml of THF is purgedwith argon and treated with 25 ml of a NaOH-solution (2 M). The mixtureis vigorously stirred for 1 h at 40° C. under argon atmosphere and thenneutralized with a HCl-solution (2 M) and extracted withdichloromethane. The combined organic layers are washed with a saturatedNaHCO₃-solution, with brine and dried over MgSO₄. The solvents areremoved and the crude compound is purified with column chromatography(silicagel; eluent: ethylacetate) and collected as a yellow oil.

[0242] Yield=5.7 g (68%) (2 steps); [a]_(D) ²⁵=+111 deg dm⁻¹ mol⁻¹ l(c=0.5 in CH₂Cl₂)

[0243]¹H-NMR (CDCl₃): δ(ppm): 8.06 (d, J=1.5 Hz, 2H), 7.93 (d, 2H), 7.38(d, 2H), 7.34 (dd, 2H), 7.04 (d, 2H), 5.18 (s, 2H), 3.11 (s, 2H)

Example 10 Synthesis ofS-6,6′-di(trimethylsilylethynyl)-2′-hexyloxy-[1,1′-binaphthalene]-2-ol11

[0244] The procedure described for 9, was followed, starting from 5.28 g(10.0 mmol) of 3. The compound is purified with column chromatography(silicagel; eluent: ethylacetate/hexane (10:90 v/v)).

Example 11 Synthesis ofS-(+)-6,6′-diethynyl-2′-hexyloxy-[1,1′-binaphthalene]-2-ol 12

[0245] The procedure, described for 10, was followed, starting from 11.The compound is purified by column chromatography (silicagel; eluent:ethylacetate/hexane (20:80 v/v) and (10:90 v/v)).

[0246] Yield=3.0 g (71%) (2 steps); [a]_(D) ²⁵=+32.0 deg dm⁻¹ mol⁻¹ l(c=1.0 in CH₂Cl₂)

[0247]¹H-NMR (CDCl₃): δ(ppm): 8.05 (d, J=1.5 Hz, 1H), 8.00 (d, J=1.5 Hz,1H), 7.96 (d, 1H), 7.82 (d, 1H), 7.44 (d, 1H), 7.32 (d, 1H), 7.29 (dd,1H), 7.21 (dd, 1H), 7.08 (d, 1H), 6.92 (d, 1H), 4.94 (s, 1H), 3.93 (m,2H), 3.09 (s, 1H), 3.05 (s, 1H), 1.43 (m, 2H), 1.0 (m, 6H), 0.75 (t, 3H)

Example 12 Compound 13

[0248] A solution of 9.65 g (50.0 mmol) of 6, 11.4 g (45.0 mmol) of I₂,5.25 g (30.0 mmol) of KIO₃ in 15 ml of H₂SO₄ (15%), 20 ml of CCl₄ and 90ml of glacial acetic acid is stirred at 75° C. for 3 h. After cooling,the precipitate is filtered, washed with cold methanol andrecrystallized twice from ethanol to give white needles.

[0249] Yield: 13.8 g (52%); T_(m): 59.8° C.

[0250]¹H-NMR (CDCl₃): δ(ppm): 7.18 (s, 2H), 3.93 (t, 4H), 1.80 (qu, 4H),1.4 (m, 12H), 0.91 (t, 6H)

Example 13

[0251] 2.65 g (5.00 mmol) of 4, 1.82 g (5.00 mmol) of 8 and 290 mg (250μmol) of Pd(0)[PPh₃]₄ are dissolved in 25 ml of dry THF. The solution ispurged with argon and 15 ml of a K₂CO₃-solution (1 M in water) is added.The reaction mixture is refluxed for two days under argon atmospherewhile vigorously stirred. After cooling down, water is added and thepolymer is extracted with dichloromethane. The polymer solution iswashed with brine, dried over anhydrous Na₂SO₄ and concentrated. Thepolymer is precipitated in methanol and filtered off. Finally, thepolymer is redissolved in THF and reprecipitated in methanol and thendried under reduced pressure.

[0252] Then, the obtained MOM-protected polymer is dissolved in 25 ml ofTHF. The solution is purged with argon and treated with 25 ml of HCl (6M). The mixture is refluxed overnight under argon atmosphere. Aftercooling down, water is added and the polymer is extracted withdichloromethane. The organic layer is washed with a saturatedNaHCO₃-solution, with brine and dried over anhydrous Na₂SO₄. The polymersolution is then concentrated and the polymer is precipitated inmethanol. After filtration and drying, the polymer is redissolved in THFand reprecipitated in methanol. This procedure is repeated twice.

[0253] Yield: 2.8 g (86%)

[0254]¹H-NMR (CDCl₃): δ(ppm): 8.13 (s, 1H), 8.09 (s, 1H), 8.04 (d, 1H),7.90 (d, 1H), 7.57 (d, 1H), 7.52 (d, 1H), 7.46 (d, 1H), 7.34 (d, 1H),7.28 (d, 1H), 7.13 (d, 1H), 7.07 (d, 2H), 4.98 (s, 1H), 3.9 (m, 6H), 1.6(m, 4H), 0.9-1.6 (m, 20H), 0.75 (t, 9H)

Example 14

[0255] A general procedure is as follows: a solution of 2.50 mmol of 13,25.0 mg of Pd[PPh₃]₂Cl₂ and 50.0 mg of PPh₃ in 10 ml of freshlydistilled piperidine and 5 ml of dry THF, is purged with argon andheated to 40° C. A purged solution of 2.50 mmol of compounds 10/12 in 10ml of dry THF is added, followed by a purged solution of 2.0 mg of CuIand 10.0 mg of LiBr in 10 ml of dry THF. The reaction mixture is stirredfor two days under reflux and inert atmosphere. After cooling down, THFis added and the polymer is precipitated in methanol. For purification,the polymer is three times redissolved in THF and reprecipitated inmethanol.

[0256] In case of PPOL 2, the reaction mixture is not diluted with THF,neither is the polymer afterwards dissolved in THF, but DMF is usedinstead.

[0257] PPOL 2:

[0258] Yield: 1.7 g (95%)

[0259]¹H-NMR (CDCl₃): δ(ppm): 7.80 (s (br), 2H), 7.74 (d, 2H), 7.18 (d,2H), 7.16 (dd, 2H), 6.95 (s, 2H), 6.94 (d, 2H), 5.41 (s, 2H), 3.93 (t,4H), 1.82 (m, 4H), 1.35 (m, 4H), 1.20 (m, 8H), 0.76 (t, 6H)

[0260] PPOL 3:

[0261] Yield: 2.3 g (86%)

[0262]¹H-NMR (CDCl₃): δ(ppm): 8.09 (d, J=1.5 Hz, 1H), 8.06 (d, J=1.5 Hz,1H), 7.98 (d, 1H), 7.86 (d, 1H), 7.46 (d, 1H), 7.38 (d, 1H), 7.33 (dd,1H), 7.29 (dd, 1H), 7.14 (d, 1H), 7.03 (s, 2H), 7.00 (d, 1H), 5.00 (s,1H), 3.9 (m, 6H), 1.82 (m, 4H), 0.9-1.6 (m, 20H), 0.86 (t, 6H), 0.75 (t,3H)

Example 16 Functionalization of Polymers

[0263] A general procedure is as follows. Prior to reaction, thechromophore is recrystallized and all reagents and solvents arethoroughly dried. For 0.333 mmol of naphthol groups (PPOL 1-3), 0.400mmol of chromophore and 0.666 ml of PPh₃ are dissolved in 15 ml of dryTHF. The mixture is purged with argon and 0.666 mmol ofdiethylazodicarboxylate (DEAD) is injected. The reaction vessel issealed (septum) and the reaction mixture is stirred for two days at roomtemperature. Then, the polymer is precipitated in methanol, filtered anddried in vacuo. Finally, the polymer is redissolved in THF, precipitatedin methanol and dried. This procedure is repeated until the filtrate isonly slightly colored.

Example 17 Synthesis of Chromophore 28

[0264] Synthesis of 2-(N-ethyl-N-phenylamino)ethanol 15

[0265] A mixture of 101 ml (800 mmol) of freshly distilledN-ethylaniline 14, 71.0 ml (1.00 mol) of 2-bromoethanol, 138 g (1.00mol) of anhydrous K₂CO₃ and 8.30 g (50.0 mmol) of anhydrous KI isdissolved in 300 ml of dry n-butanol is refluxed for four days underargon atmosphere and vigorously stirring. After cooling down, theinorganic salts are filtered off and washed with diethylether. Thesolvents are evaporated under reduced pressure and the crude reactionproduct is purified by means of a vacuum destillation.

[0266] Yield: 70.5 g (53%); b.p.: 123° C./1 mm Hg

[0267]¹H-NMR (CDCl₃): δ(ppm): 7.20 (t, 2H), 6.78 (d, 2H), 6.72 (t, 1H),3.78 (q, 2H), 3.46 (t, 2H), 3.41 (q, 2H), 1.76 (t, 1H), 1.15 (t, 3H)

[0268] Synthesis of 2-(N-ethyl-N-phenylamino)ethylethanoate 16

[0269] A mixture of 49.6 g (300 mmol) of 15 and 50 ml of acetic acidanhydride in a 250 ml-flask, equipped with a CaCl₂-tube is stirredovernight at 60° C. Then, the volatile compounds are evaporated and thecrude product is distilled under vacuüm.

[0270] Yield: 58.5 g (96%); b.p.: 129° C./0.15 mm Hg

[0271]¹H-NMR (CDCl₃): δ(ppm) : 7.21 (t, 2H), 6.72 (d, 2H), 6.68 (t, 1H),4.22 (t, 2H), 3.55 (t, 2H), 3.40 (q, 2H), 2.05 (s, 3H), 1.17 (t, 3H)

[0272] Synthesis of 2-[N-ethyl-N-(4-formylphenyl)amino]ethylethanoate 17

[0273] To 60 ml of dry DMF in a 250 ml-flask, equipped with aCaCl₂-tube, cooled in an ice bath, 29.1 (310 mmol) of OPCl₃ is dropwiseadded and the mixture is stirred for two h at 5° C. Then, 58.5 g (288mmol) of 16, dissolved in 30 ml of dry DMF, is added and the reactionmixture is stirred for 3 h at 90° C. After cooling down, the mixture ispoured into iced water, stirred for 30 min and extracted withdichloromethane. The organic layer is washed with a saturatedNaHCO₃-solution, with brine and dried over MgSO₄. After evaporation ofthe solvent, the compound is purified with column chromatography(silicagel; eluent:dichloromethane/acetonitrile (90:10 v/v)) andcollected as an oil.

[0274] Yield: 59.2 g (87%)

[0275]¹H-NMR (CDCl₃): δ(ppm): 9.74 (s, 1H), 7.73 (d, 2H), 6.74 (d, 2H),4.26 (t, 2H), 3.65 (t, 2H), 3.50 (q, 2H), 2.05 (s, 3H), 1.23 (t, 3H)

[0276] Synthesis of 4-[N-ethyl-N-(2-hydroxyethyl)amino]benzaldehyde 18

[0277] A 150 ml of NaOH-solution (5 M in water) is added to a solutionof 59.2 g (252 mmol) of 17 in 200 ml of ethanol and the mixture isstirred overnight at 40 ° C. The reaction mixture is cooled in an icebath and neutralized with HCl (5 M) and extracted with dichloromethane.The organic layer is washed with a saturated NaHCO₃-solution, with brineand dried over MgSO₄. The solvents are evaporated under reducedpressure. The product is isolated as an oil and used without furtherpurification.

[0278] Yield: 48.7 g (100%)

[0279]¹H-NMR (CDCl₃): δ(ppm): 9.68 (s, 1H), 7.67 (d, 2H), 6.72 (d, 2H),3.84 (t, 2H), 3.56 (t, 2H), 3.50 (q, 2H), 2.00 (s (br), 1H), 1.20 (t,3H)

[0280] Synthesis of2-[N-ethyl-N-[4-[2-(2-thien)ethenyl]phenyl]amino]ethanol 22

[0281] To a solution of 48.3 g (250 mmol) of 18 and 110 g (250 mmol) of21 in 500 ml of absolute ethanol, 250 ml (375 mmol) of a NaOEt-solution(1.5 M in ethanol) is dropwise added and the reaction mixture isrefluxed for 5 h under argon atmosphere. Then, the mixture is cooleddown, poured into 500 ml of iced water and extracted withdichloromethane. The combined organic layers are washed with a saturatedNaHCO₃-solution, with brine and dried over MgSO₄. After evaporation ofthe solvent, the compound is purified with column chromatography(silicagel; eluent:dichloromethane/ethylacetate (90:10 v/v)). Theproduct is isolated as a mixture of cis and trans (cis/trans 4/6).

[0282] Yield: 51.7 g (76%); Tm: 101.2° C.

[0283]¹H-NMR (CDCl₃): trans: δ (ppm): 7.34 (d, 2H), 7.10 (m, 1H), 7.03(d, J=15.7 Hz, 1H), 6.95 (m, 2H), 6.85 (d, J=15.7 Hz, 1H), 6.74 (d, 2H),3.81 (q, 2H), 3.45 (m, 4H), 1.64 (t, 1H), 1.17 (t, 3H)

[0284] cis: δ(ppm): 7.26 (d, 2H), 7.10 (m, 1H), 6.95 (m, 2H), 6.72 (d,2H), 6.54 (d, J=12.1 Hz, 1H), 6.53 (d, J=12.1 Hz, 1H), 3.81 (q, 2H),3.45 (m, 4H), 1.64 (t, 1H), 1.17 (t, 3H)

[0285] Synthesis of2-[2-[4-[N-ethyl-N-[2-[(t-butyldimethyl)silyloxy]ethyl]amino]phenyl]ethenyl]-thiophene23

[0286] In a 250 ml-flask, equipped with a CaCl₂-tube, 51.7 g (189 mmol)of 22 and 34.2 g (227 mmol) of t-butyldimethylsilylchloride aredissolved in 100 ml of dry DMF. The solution is cooled in an ice bathand 30.9 g (454 mmol) of imidazole is added in several portions. Thereaction mixture is stirred overnight at 40° C. After cooling, water isadded and the mixture is extracted with pentane. The combined organiclayers are washed with a saturated NaHCO₃-solution, with brine and driedover MgSO₄. The solvents are evaporated under reduced pressure. Theproduct is isolated as an oil and used without further purification(cis/trans 3.7/6.3).

[0287] Yield: 74.7 g (100%)

[0288]¹H-NMR (CDCl₃): trans: δ(ppm): 7.29 (d, 2H), 7.05 (m, 1H), 7.03(d, J=16.4 Hz, 1H), 6.87 (m, 2H), 6.80 (d, J=16.4 Hz, 1H), 6.74 (d, 2H),3.72 (t, 2H), 3.39 (m, 4H), 1.12 (t, 3H), 0.83 (t, 9H), 0.06 (s, 6H)

[0289] cis: δ (ppm): 7.26 (d, 2H), 7.05 (m, 1H), 6.87 (m, 2H), 6.72 (d,2H), 6.54 (d, J=12.1 Hz, 1H), 6.53 (d, J=12.1 Hz, 1H), 3.72 (t, 2H),3.39 (m, 4H), 1.12 (t, 3H), 0.83 (t, 9H), 0.06 (s, 6H)

[0290] Synthesis of2-[2-[4-[N-ethyl-N-(2-hydroxyethyl)amino]phenyl]ethenyl]thien-5-al 24

[0291] A solution of 41.8 g (108 mmol) of 23 in 300 ml of dry THF ispurged with argon, cooled to −78° C. and 94 ml (220 mmol) of n-Buli(2.34 M in hexane) is added. The solution turns dark blue. Thetemperature is slowly rised to −30° C. and 35 ml of dry DMF is added.Upon addition, the solution becomes yellow. After 2 h of stirring at−30° C., 500 ml of HCl (2 M) is added (the solution turns deep red) andthe mixture is vigorously stirred at 40° C. for 4 h. After cooling, thereaction mixture is neutralized with NH₃ (5 M) and extracted withdichloromethane. The combined organic layers are washed with a saturatedNaHCO₃-solution, with brine and dried over MgSO₄. After evaporation ofthe solvents, the compound is purified with column chromatography(silicagel; eluent:dichloromethane/ethylacetate (90:10 v/v)) andrecrystallized from chloroform/hexane. No cis-isomer is detected.

Example 18 Physical Properties

[0292] {overscore (M)}_(n)/ [α]_(D) ²⁵/ Polymer 10³ g mol⁻¹ D 10² degdm⁻¹ gm⁻¹ ml PPOL 1 7.1 2.4 1.5 PPOL 2 5.4 2.6 5.2 PPOL 3 2.3 2.3 3.8

[0293] {overscore (M)}_(n) is determined with GPC towards polystyrenestandards in THF; D={overscore (M)}_(w)/{overscore (M)}_(n)

Example 19 Electro-Optic Coefficients and Tg of Functionalized Polymers

[0294] PPOL 1 functionalized with chrom. 8 (n 32 2, FIG. 9): r₃₃=17pm/V, Tg=148° C.

[0295] PPOL 1 functionalized with chrom. 8 (n=6, FIG. 9): r₃₃=35-40 pm/V

[0296] All polymers were spincoated from 1,2,3-trichloropropane solutiononto ITO-coated glass substrates. Poling was done using a traditionalcorona set-up and nonlinear optical characterization was done bysecond-harmonic generation at a wavelength of 1064 nm. From thesemeasurements, electro-optic coefficients at 1500 nm were estimated usingthe formalism described in “D. M. Burland et al, Chem. Rev., 1994, 94,31”.

Example 20

[0297] Chiral helicene bisquinone nonracemic derivatives 41 and 51 (FIG.12) were spincoated from concentrated chloroform solutions ontohydrophobic glass slides, yielding films with thicknesses from 0.1 to0.6 microns. The resulting film had a D_(∞) symmetry with nonlinearitieson the order of 2-9 pm/V. The nonracemic form of these materialsself-aggregates into corkscrew-shaped assemblies, both in concentratedalkane solutions and in the pure material. In thin films thecorkscrew-shaped assemblies further organize into thin lamellae. Inthicker films (several tens of microns) obtained by cooling nonracemic41 and 51 from an isotropic melt, the corkscrew-shaped assembliesorganize into macroscopic fibers that are clearly visible under anoptical microscope.

[0298] Slightly thicker films (up to 1.2 microns) were prepared byheating small amounts of solid 41 and 51 between two glass slides abovethe melting point, followed by cooling to room temperature. Theresulting films are of remarkable optical quality. No macroscopic fibersare visible.

Example 21 Measurement of Second Harmonic Generation

[0299] The second-harmonic generation experiments were done byirradiating the samples at a 45° angle of incidence with a fundamentalbeam from a Nd:YAG laser (1064 nm, 50 Hz, 8 ns) and detecting thesecond-harmonic light in the transmitted direction. Half- and quarterwaveplates were used to control the polarization of the irradiatingbeam, and the second-harmonic light could be resolved into p- ands-polarized components. The nonracemic films of 41 and 51 showed afairly strong second-harmonic response, indicating that the films arenoncentrosymmetric and have at least a D_(∞) symmetry. Furthermore, thesecond-harmonic signal increases quadratically with thickness for bothfilms. FIG. 3 shows the second-harmonic signal (for a p-polarizedfundamental beam) for films of compound 41 which grows quadratically forthicknesses ranging from 0.1 to 1.2 microns.

Example 22 Physical Properties of a Chiral Substance

[0300] Heating films of 41 and 51 up to temperatures over 200° C. has nosignificant effect on their SH-efficiency. Above the melting point (211°C. for 41 and 235° C. for 51), the material becomes an isotropic liquidwith no SHG properties and the signal drops to zero. However, after thesamples are cooled to below the melting points the SH signalspontaneously return to their original values, indicating that thesamples are thermodynamically stable.

[0301] References

[0302] All publications and patents mentioned herein, are herebyincorporated by reference in their entirety as if each individualpublication or patent was specifically and individually indicated to beincorporated by reference. In case of conflict, the present application,including any definitions herein, will control.

[0303] U.S. Pat. Nos. 6,194,120; 5,290,630; 5,549,853; 6,229,047: M.Kauranen, et al. (1995) Science 470 :966; T. Verbiest et al. (1995)Science 268:1604

[0304] Equivalents

[0305] Those skilled in the art will recognize, or be able to ascertainusing no more than routine experimentation, many equivalents to thespecific embodiments of the invention described herein. Such equivalentsare intended to be encompassed by the following claims.

[0306] Unless otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in this specification and attached claimsare approximations that may vary depending upon the desired propertiessought to be obtained by the present invention. At the very least, andnot as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, each numerical parameter shouldat least be construed in light of the number of reported significantdigits and by applying ordinary rounding techniques.

[0307] Notwithstanding that the numerical ranges and parameters settingforth the broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

We claim:
 1. An optical device comprising an optically active compoundcomprising: a) a chromophore; and b) a polymer; wherein said chromophoreor said polymer is chiral; wherein said chromophore undergoesspontaneous alignment; and wherein said optical device modulates light.2. The optical device of claim 1, wherein said polymer is chiral.
 3. Theoptical device of claim 1, wherein said chromophore is chiral.
 4. Theoptical device of claim 1, wherein said optically active compound hasD_(n) symmetry, wherein n greater than or equal to
 2. 5. The opticaldevice of claim 4, wherein said optically active compound is helical. 6.The optical device of claim 2, wherein said chiral polymer comprises abinaphthyl moiety.
 7. The optical device of claim 6, wherein saidbinaphthyl moiety is selected from the group consisting of binaphthyl,binaphthol, 1,1′-binaphthyl-2-ol-2′-amine, and1,1-binaphthyl-2,2′-diamine.
 8. An optically active compound comprising:a) a polymer comprising a monomeric unit comprising a binaphthyl moiety;and b) a chromophore chemically bonded to said monomeric unit; whereinsaid optically active compound has non-centrosymmetric symmetry.
 9. Theoptically active compound of claim 8, wherein said binaphthyl moiety isselected from the group consisting of binaphthyl, binaphthol,1,1′-binaphthyl-2-ol-2′-amine, and 1,1′-binaphthyl-2,2′-diamine.
 10. Theoptically active compound of claim 8, wherein said binaphthyl moietyfurther comprises an alkyl moiety.
 11. The optically active compound ofclaim 8, wherein said binaphthyl moiety comprises an alkynyl group. 12.The optically active compound of claim 8, wherein said monomeric unit isselected from the structures represented by formulas I and II:

wherein Y represents independently for each occurrence a bond, alkyl,alkenyl, or alkynyl; R₁ represents independently for each occurrence H,alkyl, or alkoxy; R₂ represents independently for each occurrence N(R₁),O, S, Se or alkylene; R₃ represents independently for each occurrence H,alkyl, or said chromophore; R₄ represents independently for eachoccurrence H, alkyl or said chromophore; and q is in the range 1 to 7inclusive.
 13. The optically active compound of claim 12, wherein R₁ is—O-alkyl.
 14. The optically active compound of claim 13, wherein R₁ is—O-hexyl.
 15. The optically active compound of claim 8, wherein R₃ isalkyl.
 16. The optically active compound of claim 13, wherein R₃ is—O-hexyl.
 17. The optically active compound of claim 15, wherein R₂ isO.
 18. The optically active compound of claim 8, wherein R₄ is analkyl-chromophore moiety.
 19. The optically active compound of claim 8,wherein said monomeric unit is represented by the structure:

wherein Y represents independently for each occurrence alkyl or alkynyl;CHR represents said chromophore; p is in the range 0 to 7 inclusive; andq is in the range 1 to 7 inclusive.
 20. The optically active compound ofclaim 8, wherein said polymer comprises at least about five monomericunits.
 22. The optically active compound of claim 19, wherein saidpolymer comprises at least about two monomeric units.
 23. The opticallyactive compound of claim 19, wherein q is in the range of 1 to
 3. 24.The optically active compound of claim 19, wherein q is
 1. 25. Theoptically active compound of claim 19, wherein greater than about 5% ofsaid monomeric units are functionalized with a chromophore.
 26. Theoptically active compound of claim 8, wherein said monomeric unitcomprises two chromophores.
 27. The optically active compound of claim8, wherein said compound exhibits an electro-optic coefficient ofgreater than about 10 pm/V.
 28. A nonlinear optical polymer selectedfrom group consisting of formulas I and II:

wherein Y represents independently for each occurrence a bond, alkyl,alkenyl, or alkynyl; R₁ represents independently for each occurrence H,alkyl, or alkoxy; R₂ represents independently for each occurrence N(R₁),O, S, Se or alkylene; R₃ represents independently for each occurrence H,alkyl, or a chromophore; R₄ represents independently for each occurrenceH, alkyl or a chromophore; n is an integer from 1 to about 100; and q isin the range 1 to 7 inclusive.
 29. The nonlinear optical polymer ofclaim 28, wherein n is about 5 to about
 20. 30. The nonlinear opticalpolymer of claim 28, wherein R₄ is a chromophore for at least onemonomeric unit of said polymer.
 31. The nonlinear optical polymer ofclaim 29, wherein R₁ is —O-alkyl.
 32. The nonlinear optical polymer ofclaim 31, wherein R₁ is —O-hexyl.
 33. The nonlinear optical polymer ofclaim 28, wherein R₃ is alkyl.
 34. The nonlinear optical polymer ofclaim 33, wherein R₃ is —O-hexyl.
 35. The nonlinear optical polymer ofclaim 32, wherein R₂ is O.
 36. The nonlinear optical polymer of claim33, wherein R₄ is an alkyl-chromophore moiety.
 37. The nonlinear opticalpolymer of claim 33, wherein the percentage of monomeric units of saidpolymer functionalized with one or more chromophores is greater thanabout 5%.
 38. The nonlinear optical polymer of claim 33, wherein R₂ isO, and Y is an alkyl.
 39. The nonlinear optical polymer of claim 33,wherein R₂ is O, and Y is an alkynyl.
 40. The nonlinear optical polymerof claim 28, wherein said polymer is represented by the structure:

wherein CHR represents for each occurrence a chromophore; p is aninteger in the range 0 to 7 inclusive; x is 1 to about 50; and n isabout 10 to about
 50. 41. The nonlinear optical polymer of claim 28,wherein said polymer exhibits an electro-optic coefficient of greaterthan about 10 pm/V.
 42. The nonlinear optical polymer of claim 28,wherein the weight percent of chromophore is greater than about 10%. 43.A polymer composition comprising: a) a polymer comprising at least onemonomeric unit represented by formula I or II:

wherein Y represents independently for each occurrence a bond, alkyl,alkenyl, or alkynyl; R₁ represents independently for each occurrence H,alkyl, or alkoxy; R₂ represents independently for each occurrence N(R₁),O, S, Se or alkylene; R₃ represents independently for each occurrence H,alkyl, or a chromophore; R₄ represents independently for each occurrenceH, alkyl or a chromophore; q is in the range 1 to 7 inclusive; and b) achromophore.
 44. The polymer composition of claim 43, wherein saidchromophore is pendantly bound to at least one said monomeric unit.